Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors

ABSTRACT

COLOR, DIFFUSION TRANSFER PHOTOGRAPHIC ELEMENTS, FILM UNITS AND PROCESSES ARE DESCRIBED WHICH EMPLOY DYE IMAGE-PROVIDING MATERIALS WHICH ARE CLEAVABLE UPON OXIDATION IN AN ALKALINE MEDIUM TO RELEASE A DYE OR DYE PRESCURSOR WHICH DIFFUSES TO DYE IMAGE-RECEIVING LAYER. THE COMPOUNDS HAVE THE FORMULA:   1,4-(R-O-),(BALLAST)N,(DYE-O2S-)M-BENZENE   WHEREIN R IS H OR A HYDROLYZABLE ENITY, N IS 1 TO 3 AND M IS 1 TO 3.

United States Patent O" 3,698,897 DIFFUSION TRANSFER PROCESSES AND FILMUNITS COMPRISING COMPOUNDS WHICH ARE CLEAVABLE UPON OXIDATION IN ALKALIMEDIA TO PRODUCE DIFFUSIBLE DYES OR DYE PRECURSORS Thomas E. Gompf,Penfield, and Kin Kwong Lum,

Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, NY. NoDrawing. Filed July 6, 1971, Ser. No. 160,068 Int. Cl. G03c 1/40, 5/54,7/00 U.S. Cl. 96-3 21 Claims ABSTRACT OF THE DISCLOSURE Color, diffusiontransfer photographic elements, film units and processes are describedwhich employ dye image-providing materials which are cleavable uponoxidation in an alkaline medium to release a dye or dye precursor whichdiffuses to a dye image-receiving layer. The compounds have the formula:

wherein R is H or a hydrolyzable entity, n is 1 to 3 and m is 1 to 3.

This invention relates to photography and more particularly to color,diffusion transfer photography employing dye image-providing materialswhich are cleavable upon oxidation in an alkaline medium.

Color, diffusion transfer processes of the prior art such as US. Pats.2,983,606 and 3,222,169 generally involve the use of a photographicelement comprising a support, at least one silver halide emulsion layer,and contained therein or contiguous thereto, a dye developer. A liquidprocessing composition is applied to the photosensitive element andpermeates the emulsion to provide a solution of the dye developersubstantially uniformly distributed therein. As the exposed silverhalide emulsion is developed, the oxidation product of the dye developeris immobilized or precipitated in situ with the developed silver,thereby providing an imagewise distribution of unoxidized dye developerdissolved in the liquid processing composition. This immobilization isapparently due, at least in part, to a change in the solubilitycharatceristics of the dye developer upon oxidation, and particularly asregards its solubility in alkaline solutions. At least part of thisimagewise distribution of unoxidized dye developer is transferred to asuperposed image-receiving layer to provide the transfer image.

In these prior art systems, the developer moiety of the dye developer istransferred with the dye to the imagereceiving layer. In the absence ofsome further treatment, such as pH reduction with an acid, the developermoiety can undergo aerial oxidation which will have a substantial efiectupon the stability to light of the resulting dye developer image.Accordingly, it would be highly desirable to provide a transfer systemin which only the desired chemical entity, i.e., the dye, is transferredto the receiver.

In US. Pat. 3,245,789, dye developers are described which upon oxidationform an oxidation product which is more mobile and difiusible in thealkaline processing solution than is the dye developer. This patent doesnot disclose, however, the compounds of our invention which arecleavable upon oxidation in an alkaline medium.

3,698,897. Patented Oct. 17, 1972 It is therefore an object of thisinvention to provide photographic elements, film units and processes forproducing a photographic transfer image in color in which only the dyeportion of the dye image-providing material is transferred to thereceiver.

It is another object of this invention to provide a photographic systemwherein the dye portion of the dye imageproviding material which istransferred to the receiver contains a solubilizing group as a result ofcleavage in an alkaline solution.

It is another object of this invention to provide photographic systemsfor producing a photographic transfer image in color which does notrequire a post-treatment in order to obtain light stability.

It is still a further object of this invention to provide photographicsystems for producing photographic transfer images in color in which thedye image-receiving layer can either be located on a separate support orcan be located integral with the photosensitive element.

These and other objects are achieved by our invention which is describedhereinafter.

A photographic film unit according to our invention which is adapted tobe processed by passing the unit between a pair of juxtaposedpressure-applying members comprises:

(a) A photosensitive element comprising a support having thereon atleast one photosensitive silver halide emulsion layer, each silverhalide emulsion layer having associated therewith a dye image-providingmaterial comprising a compound which is cleavable upon oxidation in analkaline medium having the formula:

moiety;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render the cleavablecompound nondiffusible during development in an alkaline processingcomposition;

(3) Dye is a dye or dye precursor;

(4) n is an integer of 1 to 3; and

(5) m is an integer of 1 to 3;

(b) A dye image-receiving layer; and

(c) A rupturable container containing an alkaline processingcomposition, said container being adapted to be positioned duringprocessing of said film unit so that a compressive force applied to saidcontainer by said pressure-applying members will effect a discharge ofthe containers contents within said film unit; said film unit containinga silver halide developing agent.

A photosensitive element according to our invention is set forth in (a)in the film unit described above.

A process for producing a photographic transfer image in color accordingto our invention comprises:

(a) Treating the above-described photosensitive element with an alkalineprocessing composition in the presence of said silver halide developingagent to effect development of each of the exposed silver halideemulsion layers, thereby oxidizing the developing agent;

(b) The oxidized developing agent thereby crossoxidizing each cleavablecompound to cause the compound to cleave at the S0 linkage, thus formingan imagewise distribution of diffusible dye or dye precursor containingthe S0 moiety as a solubilizing group as a 3 function of the imagewiseexposure of each of the silver halide emulsion layers; and

At least a portion of each of the imagewise distributions of diffusibledye or dye precursor containing said solubilizing group diffusing to adye image-receiving layer to provide an image.

The photosensitive element in the above-described process can be treatedwith an alkaline processing composition to effect or initiatedevelopment in any manner. A preferred method for applying processingcomposition is by use of a rupturable container or pod which containsthe composition. In general, the processing composition employed in oursystem contains the developing agent for development although thecomposition could also just be an alkaline solution where the developeris incorporated in the photosensitive element, in which case thealkaline solution serves to activate the incorporated developer.

The dye image-receiving layer in the above-described film unit can belocated on a separate support adapted to be superposed on thephotosensitive element after exposure thereof. Such image-receivingelements are generally disclosed, for example, in U.S. Pat. 3,362,819. Arupturable container is employed and is positioned in relation to thephotosensitive element and the image-receiving element so that acompressive force applied to the container by pressure-applying members,such as would be found in a typical camera used for in-cameraprocessing, will effect a discharge of the containers contents betweenthe image-receiving element and the outermost layer of thephotosensitive element. After processing, the dye image-receivingelement is separated from the photosensitive element.

The dye image-receiving layer in the above-described film unit can alsobe located integral with the photosensitive element between the supportand the lowermost photosensitive silver halide emulsion layer. A generalformat for integral receiver-negative photosensitive elements isdisclosed in copending U.S. application Ser. No. 27,991 of Barr, Bushand Thomas filed Apr. 13, 1970 and now abandoned. In such an embodiment,the support for the photosensitive element is transparent and is coatedwith an image-receiving layer, a substantially opaque light-reflectivelayer, e.g., TiO and then the photosensitive layer or layers describedabove. After exposure of the photosensitive element, a rupturablecontainer containing an alkaline processing composition and an opaqueprocess sheet are brought into superposed position. Pressureapplyingmembers in the camera rupture the container and spread processingcomposition over the photosensitive element as the film unit iswithdrawn from the camera. The processing composition develops eachexposed silver halide emulsion layer and dye images are formed as afunction of development which diffuse to the image-receiving layer toprovide a right-reading image which is viewed through the transparentsupport on the opaque reflecting layer background. For other detailsconcerning the format of this particular integral film unit, referenceis made to the above-mentioned Barr, Bush and Thomas U.S. applicationSer. No. 27,991.

Another format for integral negative-receiver photosensitive elements inwhich the present invention can be employed is disclosed in Cole US.application Ser. No. 27,990 filed Apr. 13, 1970 and now abandoned. Inthis embodiment, the support for the photosensitive element istransparent and is coated with the image-receiving layer, asubstantially opaque, light-reflective layer, the photosensitive layeror layers described above, and a top transparent sheet. A rupturablecontainer containing an alkaline processing composition and an opacifieris positioned adjacent to the top layer and sheet. The film unit isplaced in a camera, exposed through the top transparent sheet and thenpassed throuhg a pair of pressureapplying members in the camera as it isbeing removed therefrom. The pressure-applying members rupture thecontainer and spread processing composition and opacifier over thenegative portion of the film unit to render it light-insensitive. Theprocessing composition develops each silver halide layer and dye imagesare formed as a result of development which diffuse to theimage-receiving layer to provide a right-reading image which is viewedthrough the transparent support on the opaque reflecting layerbackground. For further details concerning the format of this particularintegral film unit, reference is made to the above-mentioned Cole U.S.application Ser. No. 27,990.

In the formua listed above for our compounds which are cleavable uponoxidation in an alkaline medium, R is preferably hydrogen, although itcould be any hydrolyzable entity well-known to those skilled in the art,e.g., acetyl, mono-, dior trichloroacetyl radicals, per-fluoroacyl,pyruvyl, alkoxyacyl, nitrobenzoyl, cyanobenzoyl, sulfonyl, sulfinyl,etc.

The nature of the ballast group in the formula for the compoundsdescribed above (Ballast) is not critical as long as it confersnondiffusibility to the compounds. Typical ballast groups includelong-chain alkyl radicals linked directly or indirectly to the compoundas well as aromatic radicals of the benzene and naphthalene series, etc.Useful ballast groups generally have at least 8 carbon atoms and mayeven comprise a Dye as defined below.

In addition to Ballast and SO -Dye, the benzene nucleus in the aboveformula may be substituted with groups such as the halogens, alkyl,aryl, alkoxy, aryloxy, nitro, amino, alkylamino, arylamino, amido,cyano, alkylmercapto, keto, carboalkoxy, etc.

As previously mentioned, Dye in the above formula represents a dye ordye precursor. Such compounds are well-known to those skilled in the artand include dyes such as azo, azomethine, indoaniline, indophenol,anthraquinone, triarylmethane, alizarin, etc., and dye precursors suchas a leuco dye, a shifted dye which shifts hyposochromically orbathochromically when subjected to a different environment such as achange in pH, reaction with a material to form a complex, etc., couplerssuch as a phenol, naphthol, indazolone, open-chain benzoyl acetanilide,pivalylacetanilide, malonamide, malonanilide, cyanoacetyl coumarone,pyrazolone, compounds described in U.S. Pat. 2,756,142, etc. Examples ofsuch dyes include the following:

YELLOW DYES 4-hydroxy azobenzene 3-methy1-4-hydroxy azobenzenep-sulfhydryl azobenzene MAGENTA DYES a CH(CH3)2 OH NH-C CH3 When dyeprecursors are employed in our process instead of dyes, they areconverted to dyes by means well known to those skilled in the art eitherin the photosensitive element, in the processing composition or in thedye image-receiving layer to form a visible absorbing dye.

A preferred group of compounds 'which can be employed in our inventioninclude those having the following formula:

Ballast S Og-Dye wherein Dye and Ballast have the same definitionsdefined previously.

Compounds within this preferred formula include:

I N 0151131 --B O z-Q-NHSOz-Q-Ndfi I H CONHCH: IX: leuco shifted magentadye-providing hydroquinone OH $1 n NN-Cl CisHsi SO1 QNHK LO 1 H CONH HNH H X: Leuco shifted yellow dye-providing hydroquinone I ldlllQ- 02"@ H0 NHQ I 0 (mo 0 NH@ Br Br XI: Shifted magenta dye-providing hydroquinoneOH G1 CONH Cl Cl XII: Shifted yellow dye-providing hydroquinone XIH:Shifter cyan dye-providing hydoquinone i OH SOzQONH WNHC OCaHs f theabove compounds, especially good results are obtained with Compounds fl,IV, V, VII and VHI.

The film unit of assembly of the present invention may be used toproduce images in single or multicolors. In a three-color system, eachsilver halide emulsion layer of the film assembly will have associatedtherewith a dye image-providing material possessing a spectralabsorption range substantially complementary to the predominantsensitivity range of its associated emulsion, i.e., the bluesensitivesilver halide emulsion layer will 'have a yellow dye image-providingmaterial associated therewith, the green-sensitive silver halideemulsion layer will have a magenta dye image-providing materialassociated therewith, and the red-sensitive silver halide emulsion layerwill have a cyan dye image-providing material associated therewith. Thedye image-providing material associated with each silver halide emulsionlayer may be contained either in the silver halide emulsion layer itselfor in a layer continguous to the silver halide emulsion layer.

The concentration of the cleavable compounds that are employed in thepresent invention may be varied over a 8 wide range depending upon theparticular compound employed and the results which are desired. Forexample, cleavable dye image providing compounds of the presentinvention may be coated in layers by using coating solutions containingbetween about 0.5 and about 8 percent by weight, of the dyeimage-providing compound distributed in a hydrophilic film-formingnatural material or synthetic polymer, such as gelatin, polyvinylalcohol, etc., which is adapted to be permeated by aqueous alkalineprocessing composition.

Any silver halide developing agent can be employed in our invention aslong as it cross-oxidizes with the cleasvable compounds describedherein. The developer may be employed in the photosensitive element tobe actuated by the alkaline processing composition. Specific examples ofdevelopers which can be employed in our invention include:

Hydroquinone N-methylaminophenol Phenidone Dimezone AminophenolsN-N-diethyl-p-phenylenediamine 3-methyl-N,N-diethyl-p-phenylenediamine3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc.

In addtion, we have found that the presence of sulfite ions in theprocessing composition enhances the cleavage reaction. Such sulfite ionscan be conveniently employed in the processing composition in the formof their alkali metal salts, e.g., sodium sulfite, potassium sulfite,etc.

As was mentioned previously, the silver halide developer in our processbecomes oxidized upon development and reduces silver halide to silvermetal. The oxidized developer then cross-oxidizes the cleavable compoundcausing it to cleave at the S0 linkage, thus forming an imagewisedistribution of diifusible dye or dye precursor containing the S0solubilizing group which then diflfuses to the receiving layer toprovide the dye image. Although it is not intended to limit the presentinvention to any particular theory or reaction mechanism, it is believedthat the following chemical reactions take place according to aparticular process of the invention:

(1) Development of a latent image with h'ydroquinone, thereby oxiding itto a quinone (2) Cross-oxidation step in which quinone is reduced anddye-releasing compound is oxidized (I) OH -SOz-Dye I I Ballast oxidizerDye-releasing developer compound OH O S Og-DyB Ballast (3) Cleavage stepunder alkaline conditions to release a diffusible dye S Oz-Dy BallastOH- OH Ballast Dye- S Difiusible dye with solubilizing 0 group In usingthe cleavable compounds according to our invention, the production ofditfusible dye or dye precursor images is a function of the reduction ofdevelopable silver halide images which may involve direct or reversaldevelopment of the silver halide emulsions with a silver halidedeveloping agent. If the silver halide emulsion employed is adirect-positive silver halide emulsion, such as an internal-imageemulsion or a solarizing emulsion, which is developable in unexposedareas, a positive image can be obtained on the dye image-receivinglayer. After exposure of the film unit, the alkaline processingcomposition permeates the various layers to initiate development of theexposed photosensitive silver halide emulsion layers. The developingagent present in the film unit develops each of the silver halideemulsion-layers in the unexposed areas (since the silver halideemulsions are direct-positive ones), thus causing the developing agentto become oxidized imagewise corresponding to the unexposed areas of thedirect positive silver halide emulsion layers The oxidized developingagent then cross-oxidizes the cleavable compounds and the oxidized formof the compounds then undergoes a base-catalyzed elimination reaction torelease the preformed dyes or the dye precursors imagewise as a functionof the imagewise exposure of each of the silver halide emulsion layers.At least a portion of the imagewise distributions of diffusible dyes ordye precursors containing an S0 solubilizing group as a result ofcleavage diffuse to the image-receiving layer to form a positive imageof the original subject. After being contacted by the alkalineprocessing composition, a pH-lowering layer in the film unit orimage-receiving unit (if such a layer is needed) lowers the pH of thefilm unit or image-receiver to stabilize the image.

Internal-image silver halide emulsions useful in the above-describedembodiment are direct-positive emulsions that form latent imagespredominantly inside the silver halide grains, as distinguished fromsilver halide grains that form latent images predominantly on thesurface thereof. Such internal-image emulsions were described by Daveyet al. in U.S. Pat. 2,592,250 issued Apr. 8, 1952, and elsewhere in theliterature. Internalimage silver halide emulsions can be defined interms of the increased maximum density obtained when developed withinternal-type developers over that obtained when developed withsurface-type developers. Suitable internal-image emulsions are thosewhich, when measured according to normal photographic techniques bycoating a test portion of the silver halide emulsion on a transparentsupport, exposing to a light intensity scale having a fixed time between0.01 and 1 second, and developing for 3 minutes at 20 C. in Developer Abelow ((internal-type developer), have a maximum density at least fivetimes the maximum density obtained when an equally exposed silver halideemulsion is developed for 4 minutes at 20 C. in Developer B dmcribedbelow (surface-type developer). Preferably, the maximum density inDeveloper A is at least 0.5 density unit greater than the maximumdensity in Developer B.

10 DEVELOPER A G. Hydroquinone 15 Monomethyl-p-aminophenol sulfate 15Sodium sulfite (desiccated) 50 Potassium bromide 10 Sodium hydroxide 25Sodium thiosulfate 20 Water to make one liter.

DEVELOPER B G. p-Hydroxyphenylglycine 10 Sodium carbonate Water to makeone liter.

The solarizing direct-positive silver halide emulsions useful in theabove-described embodiment are well-known silver halide emulsions whichhave been effectively fogged either chemically or by radiation to apoint which corresponds approximately to the maximum density of thereversal curve as shown by Mees, The Theory of the Photographic Process,published by the Macmillan Co., New York, N.Y., 1942, pp. 261-297.Typical methods for the preparation of solarizing emulsions are shown byGroves British Pat. 443,245, Feb. 25, 1936, who subjected emulsions toRoentgen rays until an emulsion layer formed therefrom, when developedwithout preliminary exposure, is blackened up to the apex of itsgraduationcurve; Szaz British Pat. 462,730, Mar. 15, 1937, the use ofeither light or chemicals such as silver nitrate, organic sulfurcompounds and dyes to convert ordinary silver halide emulsions tosolarizing directpositive emulsions; and Arens U.S. Pat. 2,005,837, June25, 1935, the use of silver nitrate and other compounds in conjunctionwith heat to effect solarization. Kendall and Hill U.S. Pat. 2,541,472,Feb. 13, 1951, shows useful solarized emulsions particularly susceptibleto exposure with long wavelength light and initial development toproduce the Herschel effect described by Mees above, produced by addingbenzothiazoles and other compounds to the emulsions which are foggedeither chemically or with white light. In using the emulsions asufficient reversal image exposure is employed using minus blue light offrom about 500-700 mg wavelength, preferably 520554 m to substantiallydestroy the latent image in the silver halide grains in the region ofthe image exposure. Particularly useful are the fogged direct-positiveemulsions of Berriman U.S. Pat. 3,367,778; Illingsworth U.S. Pats.3,501,305, 3,501,306 and 3,501,- 307; and combinations thereof.

Internal-image silver halide emulsions which contain or which areprocessed in the presence of fogging or nucleating agents areparticularly useful in the above-, described embodiment since the use offogging agents in a convenient way to inject electrons into the silverhalide grains. Suitable fogging agents include the hydrazines disclosedin Ives U.S. Pats. 2,588,982 issued Mar. 11, 1952 and 2,563,785 issuedAug. 7, 1951; the hydrazides and hydrazones disclosed in Whitmore U.S.Pat. 3,227,- 552 issued Jan. 4, 1966; hydrazone quaternary saltsdescribed in Lincoln and Heseltine application Ser. No. 828,064, filedApr. 28, 1969, now abandoned; or mixtures thereof. The quantity offogging agent employed can be widely varied depending upon the resultsdesired. Generally, the concentration of fogging agent is from about 1to about 20 mg. per square foot of photosensitive layer in thephotosensitive element or from about 0.1 to about 2 grams per liter ofdeveloper if it is located in the developer.

Other embodiments in which our imaging chemistry can be employed includethe techniques described in U.S. Pats. 3,227,550; 3,227,551; 3,227,552;and in British Pat. 904,364, page 19, lines 1-41, wherein our dyeimageproviding materials are substituted for the nondiifusible couplersdescribed therein. For example, a film unit using developmentinhibitor-releasing couplers as described in U.S. Pat. 3,227,551 may beemployed in conjunction with the dye image-providing materials describedherein. In this method, however, the developing agent employed isrestricted to one which oxidatively couples to release the inhibitorcompounds. These developing agents are generally selected from the classof aromatic primary amino developing agents such as p-aminophenols orp-phenylenediamines.

Another embodiment of our invention uses the imagereversing techniquedisclosed in British Pat. 904,364, page 19, lines 1-41. In this systemour cleavable compounds are used in combination with physicaldevelopment nuclei in a nuclei layer contiguous to the photosensitivesilver halide emulsion layer. The film unit contains a silver halidesolvent, preferably in a rupturable container with the alkalineprocessing composition, and the photosensitive element contains animmobilizing coupler, which is capable of reacting with oxidizeddeveloper to form an immobile product. This embodiment also restrictsthe choice of developing agents to one which is reactive with theimmobilizing coupler. Preferred compounds include the primary aromaticamines described above.

Spectral-sensitizing dyes can be used conveniently to confer additionalsensitivity to the light-sensitive silver halide emulsion of themultilayer photographic elements of the invention. For instance,additional spectral sensitization can be obtained by treating theemulsion with a solution of a. sensitizing dye in an organic solvent orthe dye may be added in the form of a dispersion as described in Owenset al., British Pat. 1,154,781 issued June 11, 1969. For optimumresults, the dye can either be added to the emulsion as a final step orat some earlier stage.

Sensitizing dyes useful in sensitizing such emulsions are described, forexample, in Brooker et al., U.S. Pat. 2,526,632, issued Oct. 24, 1950;Sprague, U.S. Pat. 2,503,- 776, issued Apr. 11, 1950; Brooker et al.,U.S. Pat. 2,493,- 748, issued Jan. 10, 1950; and Taber et al., U.S. Pat.3,3 84,486 issued May 21, 1968. Spectral sensitizers which can be usedinclude the cyanines, merocyanines, complex (trior tetranuclear)merocyanines, complex (tri-or tetranuclear) cyanines, holopolarcyanines, styryls, hemicyanines (e.g. enamine hemicyanines), oxonols andhemioxonols. Dyes of the cyanine classes can contain such basic nucleias the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles,thiazoles, selenazoles and imidazoles. Such nuclei can contain alkyl,alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enaminegroups and can be fused to carbocyclic or heterocyclic ring systemeither unsubstituted or substituted with halogen, phenyl, alkyl,haloalkyl, cyano, or alkoxy groups. The dyes can be symmetrical orunsymmetrical and can contain alkyl, phenyl, enamine or heterocyclicsubstituents on the methine or polymethine chain. The merocyanine dyescan contain the basic nuclei mentioned above as well as acid nuclei suchas thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones,barbituric acids, thiazolineones, and malononitrile. These acid nucleican be substituted with alkyl, alkylene, phenyl, carboxyalkyl,sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylarnino groups, orheterocyclic nuclei. Combinations of these dyes can be used, if desired.In addition, supersensitizing addenda which do not absorb visible lightcan be included, for instance, ascorbic acid derivatives, azaindenes,cadimum salts, and organic sulfonic acids as described in McFall et al.,U.S. Pat. 2,933,390 issued Apr. 19, 1960 and Jones et al., U.S. Pat.2,937,089 issued May 17, 1960.

The various silver halide emulsion layers of a color film assembly ofthe invention can be disposed in the usual order, i.e., theblue-sensitive silver halide emulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer or a Carey Leasilver layer can be present between the blue-sensitive andgreen-sensitive silver halide emulsion layer for absorbing 12 orfiltering blue radiation that may be transmitted through theblue-sensitive layer. If desired, the selectively sensitized silverhalide emulsion layers can be disposed in a different order, e.g., theblue-sensitive layer first with respect to the exposure side, followedby the red-sensitive and green-sensitive layers.

The silver halide emulsions used in this invention can comprise, forexample, silver chloride, silver bromide, silver chlorobromide, silverbromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsionscan be coarseor fine-grain and can be prepared by any of the well-knownprocedures, e.g., single-jet emulsions such as those described inTrivelli and Smith, The Photographic Journal, vol. LXXIX, May 1939 (pp.330-338), doublejet emulsions, such as Lippmann emulsions, ammoniacalemulsions, thiocyanate or thioether ripened emulsions such as thosedescribed in Nietz et al., U.S. Pat. 2,222,264 issued Nov. 19, 1940;Illingsworth, U.S. Pat. 3,320,069 issued May 16, 1967; and McBride U.S.Pat. 3,271,157 issued Sept. 6, 1966. Surface-image emulsions can be usedor internal-image emulsions can be used such as those described in Daveyet al., U.S. Pat. 2,592,250 issued May 8, 1952; Porter et al., U.S. Pat.3,206,313 issued Sept. 14, 1965; Berriman, U.S. Pat. 3,367,778 issuedFeb. 6, 1968; and Bacon et al., U.S. Pat. 3,447,927 issued June 3, 1969.The emulsions may be regular-grain emulsions such as the type describedin Klein and Moisar, J. Phot. Sci., vol. 12, No. 5, September/ October,1964, (pp. 242-251). Negative-type emulsions may be used ordirect-positive emulsions may be used such as those described inLeermakers, U.S. Pat. 2,184,013 issued Dec. 19, 1939; Kendall et al.,U.S. Pat. 2,541,472 issued Feb. 13, 1951; Berriman, U.S. Pat. 3,367,778issued Feb. 6, 1968; Schouwenaars, British Pat. 723,019 issued Feb. 2,1955; Illingsworth et al., French Pat. 1,520,821 issued Mar. 4, 1968;Illingsworth, U.S. Pat. 3,501,307 issued Mar. 17, 1970; Ives, U.S. Pat.2,563,785 issued Aug. 7, 1951 Kuott et al., U.S. Pat. 2,456,953 issuedDec. 21, 1948; and Land, U.S. Pat. 2,861,885 issued Nov. 25, 1958.

The emulsions used with this invention may be sensitized with chemicalsensitizers, such as with reducing agents; sulfur, selenium or telluriumcompounds; gold, platinum or palladium compounds; or combinations ofthese. Suitable procedures are described in Sheppard et al., U.S. Pat.1,623,499 issued Apr. 5, 1927; Waller et al., U.S. Pat. 2,399,083 issuedApr. 23, 1946; McVeigh, U.S. Pat. 3,297,447 issued Jan. 10, 1967; andDunn, U.S. Pat. 3,297,446 issued Jan. 10, 1967.

The silver halide emulsions used with this invention may contain speedincreasing compounds such as polyalkylene glycols, cationic surfaceactive agents and thioethers or combinations of these as described inPiper, U.S. Pat. 2,886,437 issued May 12, 1959; Damn et al., U.S. Pat.3,046,134 issued July 24, 1962; Carroll et al., U.S. Pat. 2,944,900issued July 12, 1960; and Goife, U.S. Pat. 3,294,540 issued Dec. 27,1966.

The silver halide emulsions used in the practice of this invention canbe protected against the production of fog and can be stabilized againstloss of sensitivity during keeping. Suitable antifoggants andstabilizers each used alone or in combination include thiazolium saltsdescribed in Brooker et al., U.S. Pat. 2,131,038 issued Sept. 27, 1938;and Allen et al., U.S. Pat. 2,694,716 issued Nov. 16, 1954; theazaindenes described in Piper, U.S. Pat. 2,886,437 issued May 12, 1959;and Heimbach et al., U.S. Pat. 2,444,605 issued July 6, 1948; themercury salts as described in Allen et al., U.S. Pat. 2,728,663 issuedDec. 27, 1955 the urazoles described in Anderson et al., U.S. Pat.3,287,135 issued Nov. 22, 1966; the sulfocatechols described in Kennardet al., U.S. Pat. 3,236,652 issued Feb. 22, 1966; the oximes describedin Carroll et al., British Pat. 623,448 issued May 18, 1949; nitron;nitroindazoles; the mercaptotetrazoles described in Kendall et al., U.S.Pat. 2,403,927 issued July 16, 1946; Kennard et al., U.S. Pat. 3,266,897issued Aug. 16, 1966;

13 and Luckey et al., U.S. Pat. 3,397,987 issued Aug 20, 1968; thepolyvalent metal salts described in Jones, U.S. Pat. 2,839,405 issuedJune 17, 1958; the thiuronium salts described in Herz et al., U.S. Pat.3,220,839 issued Nov. 30, 1965 the palladium, platinum and gold saltsdescribed in Trivelli et al., U.S. Pat. 2,566,263 issued Aug. 28, 1951;and Yutzy et al., U.S. Pat. 2,597,915 isused May 27, 1952.

The rupturable container employed in this invention can be of the typedisclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 2,653,732; 2,723,051;3,056,492; 3,056,491 and 3,152,,515. In general such containers comprisea rectangular sheet of fluid and air-impervious material foldedlongitudinally upon itself to form two walls which are sealed to oneanother along their longitudinal and end margins to form a cavity inwhich processing solution is contained.

In a color film unit according to this invention each silver halideemulsion layer containing a dye image-providing material or having thedye image-providing material present in a contiguous layer may beseparated from the other silver halide emulsion layers in the negativeportion of the film unit by materials including gelatin, calciumalginate, or any of those disclosed in U.S. Pat. No. 3,384,483,polymeric materials such as polyvinylamides as disclosed in US. Pat.3,421,892, or any of those disclosed in French Pat. 2,028,236 or U.S.Pat. Nos. 2,992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263;3,069,264; 3,121,001; and 3,427,158.

Generally speaking, except where noted otherwise, the silver halideemulsion layers in the invention comprise photosensitive silver halidedispersed in gelatin and are about 0.6 to 6 microns in thickness; thedye image-providing materials are dispersed in an aqueous alkalinesolution-permeable polymeric binder, such as gelatin, as a separatelayer about 1 to 7 microns in thickness; and the alkalinesolution-permeable polymeric interlayers, e.g., gelatin, are about 1 tomicrons in thickness. Of course these thicknesses are approximate onlyand can be modified according to the product desired. In addition togelatin, other suitable hydrophilic materials which can be employedinclude both naturally-occurring substances such as proteins, e.g.,gelatin derivatives, cellulose derivatives, polysaccharides such asdextran, gum arabic and the like; and synthetic polymeric substancessuch as water soluble polyvinyl compounds like poly(vinylpyrrolidone),acrylamide polymers and the like.

The photographic emulsion layers and other layers of a photographicelement employed in the practice of this invention can also containalone or in combination with hydrophilic, water-permeable colloids,other synthetic polymeric compounds such as dispersed vinyl compoundssuch as in latex form and particularly those which increase thedimensional stability of the photographic materials. Suitable syntheticpolymers include those de scribed for example, in Nottorf, U.S. Pat.3,142,568 issued July 28, 1964; White, U.S. Pat. 3,193,386 issued July6, 1965; Houck et al., U.S. Pat. 3,062,674 issued Nov. 6, 1962; Houck etal., U.S. Pat. 3,220,844 issued Nov. 30, 1965', Ream et al., US. Pat.3,287,289 issued Nov. 22, 1966; and Dykstra, U.S. Pat. 3,411,911 issuedNov. 19, 1968. Particularly effective are those water-insoluble polymersof alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylatesor methacrylates, those which have cross-linking sites which facilitieshardening or curing described in Smith, U.S. Pat. 3,488,708 issued Jan.6, 1970, and those having recurring sulfobetaine units as described inDykstra, Canadian Pat. 774,054.

Any material can be employed as the image-receiving layer in thisinvention as long as the desired function of mordanting or otherwisefixing the dye images will be obtained. The particular material chosenwill, of course, depend upon the dye to be mordanted. If acid dyes areto be mordanted, the image-receiving layer can contain basic polymericmordants such as polymers of amino guanidine derivatives of vinyl methylketone such as described in Minsk, U.S. Pat. 2,882,156 issued Apr. 14,1959, and basic polymeric mordants such as described in copending U.S.application Ser. No. 100,491 of Cohen et al. filed Dec. 21, 1970. Othermordants useful in our invention include poly-4-vinylpyridine, the2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compoundsdescribed in Sprague et al., U.S. Pat. 2,484,430 issued Oct. 11, 1949,and cetyl trimethylammonium bromide, etc. Effective mordantingcompositions are also described in Whitmore, U.S. Pat. 3,271,148 andBush, U.S. Pat. 3,271,147, both issued Sept. 6, 1966.

Furthermore, the image-receiving layer can be suflicient by itself tomordant the dye as in the case of use of an alkaline solution-permeablepolymeric layer such as N-methoxymethyl polyhexylmethylene adipamide;partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with orwithout plasticizers; cellulose acetate; gelatin; and other materials ofa similar nature. Generally, good results are obtained when theimage-receiving layer, preferably alkaline solution-permeable, istransparent and about 0.25 to about 0.04 mil in thickness. Thisthickness, of course, can be modified depending upon the result desired.The image-receiving layer can also contain ultraviolet absorbingmaterials to protect the mordanted dye images from fading due toultraviolet light, brightening agents such as the stilbenes, coumarins,triazines, oxazoles, dye stabilizers such as the chromanols,alkylphenols, etc.

Use of a pH-lowering material in the dye image-receiving element of afilm unit according to the invention will usually increase the stabilityof the transferred image. Generally, the pH-lowering material willeffect a reduction in the pH of the image layer from about 13 or 14 toat least 11 and preferably 5-8 within a short time after imbibition. Forexample, polymeric acids as disclosed in U.S. Pat. 3,362,819 or solidacids or metallic salts, e.g., zinc acetate, zinc sulfate, magnesiumacetate, etc., as disclosed in U.S. Pat. 2,584,030 may be employed withgood results. Such pH-lowering materials reduce the pH of the film unitafter development to terminate development and substantially reducefurther dye transfer and thus stabilize the dye image.

An inert timing or spacer layer can be employed in the practice of ourinvention over the pH-lowering layer which times or controls the pHreduction as a function of the rate at which alkali diffuses through theinert spacer layer. Examples of such timing layers include gelatin,polyvinyl alcohol or any of those disclosed in U.S. Pat. 3,455,686. Thetiming layer is also effective in evening out the various reaction ratesover a wide range of temperatures, e.g., premature pH reduction isprevented when imbibition is effected at temperatures above roomtemperature, for example, at to F. The timing layer is usually about 0.1to about 0.7 mil in thickness. Especially good results are obtained whenthe timing layer comprises a hydrolyzable polymer or a mixture of suchpolymers which are slowly hydrolyzed by the processing composition.Examples of such hydrolyzable polymers include polyvinyl acetate,polyamides, cellulose esters, etc.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., sodiumhydroxide, sodium carbonate or an amine such as diethylamine, preferablypossessing a pH in excess of 12, and preferably containing a developingagent as described previously. The solution also preferably contains aviscosity-increasing compound such as a high molecular-weight polymer,e.g., a water-soluble ether inert to alkaline solutions such ashydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulosesuch as sodium carboxymethy cellulose. A concentration ofviscosity-increasing compound of about 1 to about 5% by weight of theprocessing composition is preferred which will impart thereto aviscosity of about 100 c.p.s. to about 200,000 c.p.s. In certainembodiments of our invention, an opacifying agent, e.g., TiO carbonblack, etc., may be added to the processing composition.

While the alkaline processing composition used in this invention can beemployed in a rupturable container, as described previously, toconveniently facilitate the introduction of processing composition intothe film unit, other methods of inserting processing composition intothe film unit could also be employed, e.g., interjecting processingsolution with communicating members similar to hypodermic syringes whichare attached either to a camera. or camera cartridge.

The alkaline solution-permeable, substantially opaque, light-reflectivelayer employed in certain embodiments of photographic film units of ourinvention can generally comprise any opacifier dispersed in a binder aslong as it has the desired properties. Particularly desirable are whitelight-reflective layers since they would be esthetically pleasingbackgrounds on which to view a transferred dye image and would alsopossess the optical properties desired for reflection of incidentradiation. Suitable opacifying agents include titanium dioxide, bariumsulfate, zinc oxide, barium stearate, silver flake, silicates, alumina,zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate,kaolin, mica, or mixtures thereof in widely varying amounts dependingupon the degree of opacity desired. The opacifying agents may bedispersed in any binder such as an alkaline solution-permeable polymericmatrix such as, for example, gelatin, polyvinyl alcohol, and the like.Brightening agents such as the stilbenes, coumarins, triazines andoxazoles can also be added to the light-reflective layer, if desired.When it is desired to increase the opacifying capacity of thelight-reflective layer, dark-colored opacifying agents, e.g., carbonblack, nigrosine dyes, etc., may be added to it, or coated in a separatelayer adjacent to the light-reflective layer.

The supports for the photographic elements of this invention can be anymaterial as long as it does not deleteriously affect the photographicproperties of the film unit and is dimensionally stable. Typicalflexible sheet materials include cellulose nitrate film, celluloseacetate film, poly(vinyl acetal) film, polystyrene film,poly(ethyleneterephthalate) film, polycarbonate film, poly-a-olefinssuch as polyethylene and polypropylene film, and related films orresinous materials as well as glass, paper, metal, etc. The support isusually about 2 to 6 mils in thickness.

While the invention has been described with reference to layers ofsilver halide emulsions and dye image-providing materials, dotwisecoating, such as would be obtained using a gravure printing technique,could also be employed. In this technique, small dots of blue-, greenandred-sensitive emulsions have associated therewith, respectively, dots ofyellow, magenta and cyan color-providing substances. After development,the transferred dyes would tend to fuse together into a continuous tone.

The photographic layers employed in the practice of this invention maycontain surfactants such as saponin; anionic compounds such as the alkylaryl sulfonates described in Baldsiefen, U.S. Pat. 2,600,831 issued June17, 1952; amphoteric compounds such as those described in Ben-Ezra, U.S.Pat. 3,133,816 issued May 10, 1964; and water-soluble adducts ofglycidal and an alkyl phenol such as those described in Olin Mathieson,British Pat. 1,022,878 issued Mar. 16, 1966; and Knox, U.S. Pat.3,514,293 issued May 26, 1970.

The various layers, including the photographic layers, employed in thepractice of this invention can contain light-absorbing materials andfilter dyes such as those described in Sawdey, U.S. Pat. 3,253,921issued May 31, 1966; Gaspar, U.S. Pat. 2,274,782 issued Mar. 3, 1942;Silberstein et a1. U.S. Pat. 2,527,583 issued Oct. 31,1950; andVanCampen, U.S. Pat. 2,956,879 issued Oct. 18, 1960.

The sensitizing dyes and other addenda used in the practice of thisinvention can be added from water solutions or suitable organic solventsolutions may be used. The compounds can be added during variousprocedures including those described in Collins et al., U.S. Pat.2,912,343 issued 16 Nov. 10, 1959; McCrossen eta1., U.S. Pat. 3,342,605issued Sept. 19, 1967; Audran, U.S. Pat. 2,996,287 issued Aug. 15, 1961and Johnson et al., U.S. Pat. 3,425,835 issued 'Feb. 4, 1969.

The photographic layers used in the practice of this invention may becoated by various coating procedures including dip coating, air knifecoating, curtain coating, or extrusion coating using hoppers of the typedescribed in Beguin, U.S. Pat. 2,681,294 issued June 25, 1954. Ifdesired, two or more layers may be coated simultaneously by theprocedures described in Russell, U.S. Pat. 2,761,- 791 issued Sept. 4,1956; Hughes, U.S. Pat. 3,508,947 issued Apr. 18, 1970; and Wynn,British Pat. 837,095 issued June 9, 1960. This invention also can beused for silver halide layers coated by vacuum evaporation as describedin British Pat. 968,453 issued Sept. 2, 1964, and LuValle et al., U.S.Pat. 3,219,451 issued Nov. 23, 1965.

The photographic and other hardenable layers used in the practice ofthis invention can be hardened by various organic or inorganichardeners, alone or in combination, such as the aldehydes, and blockedaldehydes as described in Allen et al., U.S. Pat. 3,232,764 issued Feb.1, 1966; ketones, carboxylic and carbonic acid derivatives, sulfonateesters, sulfonyl halides and vinyl sulfonyl ethers as described inBurness et al., U.S. Pat. 3,539,644 issued Nov. 10, 1970; active halogencompounds, epoxy compounds, aziridines, active olefines, isocyanates,carbodiimides, polymeric hardeners such as oxidized polysaccharides likedialdehyde starch and oxyguargum and the like.

The following examples further illustrate the invention.

EXAMPLE 1 01,113, SO2NO1 sow-Nor To separate the pure isomer A, thehydroquinone is allowed to react with chloroacetic anhydride on a steambath. Only isomer A forms the monochloroacetate and this is separated bychromatography on silica gel. The chloroacetate is hydrolyzed withHCl-saturated ethanol at 35 C.

3,698,897 17 18 EXAMPLE 2.P-REPARATION OF COMPOUND I OH:

on ia u z- Compound I A 4.0 g. portion of Compound A in 100 ml. oftetrahydrofuran is reduced over palladium on carbon at two atmosphereshydrogen pressure in a Parr (Trademark) shaker. The solvent is removedin vacuo and the residual gum (B) is dissolved in 20 ml. of dry dioxane.To this are added 2.0 g. of 4-phenylazobenzoyl chloride followed by 2.0ml. of quinoline. The mixture is stirred at ambient temperature for 24hours, poured into water, and the resulting gum washed several timeswith water by decantation. The gum is dissolved in acetonitrile and ayellow solid crystallizes after scratching. The solid mixture isdissolved in chloroform and poured into a silica gel column and thendeveloped with chloroform to remove certain impurities. The desiredproduct is removed from the column with a mixture of 10% methanol-90%chloroform and recrystallized from chloroform to yield fine yellowplates of 3-[4-(4-phenylazobenzamido)phenylsulfonyl]-5-pentadecylhydroquinone(Compound I), M.P. 155- EXAMPLE 3.--PREPARATION OF COMPOUND IV A020 152NOz 15 31 O C 0 CH3 0 1) Reduce 2) Dlazotize C15H3| -SO -NO2 3) CoupleO O C H: (C) O C 0 CH3 0151131 -SO --N=N A C 0 CH3 C H C 3) 2 CH(CH3):

Preparation of 3- (4-niflrophenylsulfonyl)-5-pentadecylhydroquinonediacetate (C) A 3.0 g. sample of Compound A is heated on a steam bathwith a mixture of 10 ml. acetic anhydride and 1 drop of concentrated H50 After 1 hour, the mixture is poured into 200 ml. water at 60 C., heldat 60 C. for 5 minutes and then cooled. The supernatant liquid isremoved by decantation and the residual gum is crystallized from amixture of aoetonitrile and ethanol to yield 2.9' g. of the diacetate,M.P. 77.5-78.5 C.

Preparation of3-[4-(1-hydroxy-4-isopropoxy-2-naphthylazo)phenylsulfonyl]-5-pentadecylhydroquinonediacetate (D) Compound C (2.8 g.) is reduced in 100 ml. tetrahydrofuranover palladium on carbon. After filtering off the catalyst and removingthe solvent in vacuo, a gum remains. This is dissolved at 15 C. in 40ml. of acetate acid to which 1.3 ml. H and 0.35 g. NaNO are added. Afterstirring for 15 minutes, another 1.0 ml. H 80 followed by 0.1 g. NaNOand 5 ml. chloroform, is added and dissolution results soon thereafter.The solution is added at 0 C. to a stirred solution of 1.1 g. of4-isopropoxynaphthol in 70 ml. of pyridine mixed with 70 ml. ofmethanol. The mixture is stirred overnight and 30 ml. of water are addedto precipitate a magenta dye which, after recrystallization frommethanol, yields 0.6 g. of product, M.P. 149-l51 C.

Compound D (0.5 g.) is hydrolyzed under nitrogen in a mixture of 15 ml.ethanol, 50 ml. H 0 and 1 g. of 50% NaOH. After 35 minutes at 65 C., itis acidified with acetic acid, collected and recrystallized from ethanolto yield 0.25 g. of Compound IV, M.P. 159-1 63 C.

EXAMPLE 4.P-REPARATION OF COMPOUND V H2804, NaNO, 0151131 -SO,...NHS

OH I l O N 15 121 SOQQ N I Pyridine L- N in MeOH NHCH;

o --N can -so,

NHOH

To a solution of 20.0 g. (0.042 mol.) of Compound B in 20 ml. of DMF areadded 400 ml. of glacial acetic acid and 400 ml. of propionic acid. Themixture is cooled to C. in an ice-Water bath, 12.0 g. concentrated H 80are added, followed by the dropwise addition of 2.6 g. (0.038 mol.)sodium nitrite dissolved in 5 ml. water. The mixture is immediatelypoured with stirring into a solution (at 0 C.) of 9.1 g. (0.042 mol.) of1-phenyl-3-methylcarbamoyl-S-pyrazolone in 400 ml. pyridine and 800 ml.methanol. The solution is evaporated to about 200 ml. and poured into 1liter of cold water with vigorous stirring. The yellow solid is filteredand dried. The crude product is dissolved in 50 ml. acetone and allowedto stand at room temperature. A yellow, crystalline product, 16 g.(54%), is obtained. The product is recrystallized from ethyl acetate toyield Compound V, MJP. 155-157 C.

In 50 ml. dry dioxan are mixed 2.3 g. (4.6 mmols.) of2-chloro-3-(4-aminophenylsulfonyl) 5 pentadecylhydroquinone, 2.0 g. (5.0mmols.) of 4-(1 phenyl-3-methylcarbamoyl 4pyrazoline-S-onlyazo)phenylsulfonyl chloride and 0.4 g. (5.1 mmols.) ofpyridine. The mixture is refluxed for 18 hours, then poured into coldWater. The resulting solid is filtered, dried, dissolved in chloroformand the dye isolated by chromatography on silica gel. Onecrystallization from ethanol yields 1.5 g. M.P. 171-173 C.

EXAMPLE 6.P'REPARATION OF COMPOUND VII Preparation of3-(3-carboxyphenylsulfonyl)-5-pentadecylhydroquinone benzylcarbonate (E)C1COOCIIZCEH5 i (JOOH OCOOCHzC Ih CISHM Preparation of 3 [3 (3 hydroxy 4benzamidophenylcarbamoyl)phenylsulfonyl] S-pentadecylhydroquinonebenzylcarbonate (G) OC 0 O CHgCal-I;

SOClz H (E) (10 OH ()0 O O CH2CaH I Q e iaHal OH (F) O0 O1 ONHCHa O I T:N

CONHCHa ()C O 0 CH2C5H5 isHai S0z NHCOCaHs (5H JZONH A S-g. portion ofCompound E in 10 ml. of thionyl chloride and 30 ml. of chloroform isrefluxed for 1 hour and the solvents removed in vacuo. The resulting gum(Compound F) is dissolved in 30 ml. dry dioxane and then 5 g. of2-benzamido-S-aminophenol and 4 g. of quinoline are added. The mixtureis stirred at ambient temperature for 1 hour and then heated in thesteam bath for 15 minutes. It is poured into ice water, the resultinggum washed by decantation and then dissolved in a hexanechloroformmixture. After drying (MgSO a gummy solid forms slowly. Tworecrystallizations from an ethanol-methanol mixture yields 6 g. ofsolid, Compound G, M.P. 123-133 C.

Preparation of 3 {3 [3 oxo 4 benzamido 6 -(4 hydroxy 3,5dichlorophenylimino)cyclohexadienylcarbamoylJphenylsulfonyl} 5pentadecylhydroquinone benzylcarbonate (H) (f0 0 O CHzCaH;

(TH I C 5H31 SO NHCOCfiHa H (BONE NC I ll C1 C1 15 31 SOQ H ONH is l@Qwr (H) H A 3.2-g. (3.8 mmol.) portion of Compound G is mixed in 300ml. tetrahydrofuran with 0.8 g. (3.8 mmol.) of 2,6-dichloro-4-N-chloroquinoneimine at room temperature. To this is addedwith stirring a solution of 2.0 g. of sodium bicarbonate in 300 ml. ofwater and 100 ml. of ethanol. After stirring at ambient temperature for1 hour, the solution is acidified with acetic acid and diluted with 800ml. water. The mixture is extracted with chloroform, the extracts washedwith water and dried (MgSO The desired dye is separated bychromatography on silica gel and recrystallized from acetonitrile toyield 1.6 g. of Compound H, M.P. 138l48 C.

O C O O CHr e s N l e g-o1 0 n I 0.51131 -s02 -NHC 0 our,

on (IJONH I ClQ-Ol Compound VII H A 3.4-g. sample of Compound H isreduced over palladium on carbon in a mixture of 100 m1. ethanol, 100ml. tetrahydrofuran and 1 ml. acetic acid. The catalyst is filtered offand the solvents removed in vacuo. The resulting gum is crystallizedfrom acetonitrile to yield 1.5 g. of grayish yellow solid of CompoundVII, M.P. 167-175 C.

EXAMPLE 7 A single-layer, light-sensitive element is prepared bydissolving 0.3 g. of Compound I in 0.6 ml. of diethyl lauramide and 3.0ml. of 2-methyltetrahydrofuran. The solution is dispersed in 15.5 ml. ofaqueous gelatin with a colloid mill. One ml. of tri-isopropylnaphthalene sulfomate as a 5% solution is added to aid in dispersion. Tothis is added 3 ml. of a gelatin-silver bromide emulsion and 1.0 ml. ofa 7 /2% solution of the spreading agent saponin. The volume of themixture is adjusted with water and 10% CISHH NHC O C' -H gelatin andcoated on a support such that about 32x 10- moles/ft. of silver ispresent and there are 6 moles of silver coated for every 1 mole ofCompound I.

A sample of the photosensitive element is exposed to a graduated-densitymulticolor test object. A processing composition comprising Phenidone(0.25 g./l.), NaOH (1 normal), Na SO (25 g./1.) andhydroxyethylcellulose (3O g./l.) is employed in a pod and is spreadbetween the exposed surface of the photosensitive element and asuperposed dye image-receiving element comprising a support coated with700 mg./ft. of gelatin and mg./ft. of the mordantN-n-octadecyl-tri-butylammonium bromide, by passing the transfersandwich between a pair of juxtaposed pressure rollers.

After 60 seconds at about 24 C., the film unit is separated. A negativeyellow dye image is observed on the dye image-receiving sheet.

EXAMPLE 8 A photosensitive element is prepared by coating on an opaquecellulose acetate film support a negative-working gelatin-silverchlorobromide emulsion (150 mg. gelatin/ ft. and 60 mg. silver/ft?)andmagenta cleavable Compound IV,3-[4-(1-hydroxy-4-isopropoxy-Z-naphthylazo)phenylsulfonyl]-5-pentadecylhydroquinone (60 mg./ft.

A dye image-receiving element is prepared by coating anN-n-hexadecyl-N-morpholinium ethosulfate/methyl-trin-dodecylammoniump-toluenesulfonate coacervate mordant dispersion of the type describedin US. Pat. 3,271,- 147 of Bush issued Sept. 6, 1966, on an opaquesupport.

A sample of the photosensitive element is exposed to a graduated-densitymulticolor test object. The following processing composition is employedin a pod and is spread between the exposed surface of the photosensitiveelement and the superposed dye image-receiving element by passing thetransfer sandwich between a pair of juxtaposed pressure rollers:

G. Sodium hydroxide 40 Sodium sulfite 20 Hydroxyethylcellulose 25Phenidone 1.5

Water to 1000 ml.

After 60 seconds at about 25 C., the dye image-receiving element isseparated from the negative element. A negative, magenta dye image isobserved on the dye imagereceiving element.

EXAMPLE 9 The procedure of Example 8 is repeated except that theprocessing composition does not contain Phenidone. No visible dye imagein the receiving element is obtained and no visible silver developmenttakes place in the negative element. This example illustrates that thecleavable compounds of our invention are incapable of developmentthemselves and require a separate silver halide developing agent in thesystem.

EXAMPLE 10 A photosensitive element is prepared by coating on an opaquecellulose acetate film support a negative-working gelatin-silverchlorobromide emulsion (150 mg. gelatin/ ft. and 87 mg. silver/ft?) andyellow cleavable Compound V,3-[4-(1-phenyl-3-methylcarbamoyl-4-pyrazolin- 5 ony1azo)phenylsulfonyl]5 pentadecylhydroquinone (93.5 mg./ft.

This element is exposed and processed as in Example 8 to obtain anegative, yellow dye image on the dye image-receiving element.

EXAMPLE 11 The procedure of Example 10 is repeated except that theprocessing composition does not contain Phenidone. No visible dye imagein the receiving element is obtained and no visible silver developmenttakes place in the negative element. This example illustrates that thecleavable 23 compounds of our invention are incapable of developmentthemselves and require a separate silver halide developing agent in thesystem.

EXAMPLE 12 A multilayer, multicolor photosensitive element is preparedby coating the following layers in the order recited on an opaquecellulose acetate film support:

(1) red-sensitive, negative-working, gelatin-silver chlorobromideemulsion (150 mg. gelatin/ft. and 87 mg. silver/ft?) and yellowcleavable Compound V, 3-[4-(1- phenyl 3 methylcarbamoyl4-pyrazolin-5-onylazo) phenylsulfonyl]-5-pentadecylhydroquinone (93.5mg./ ft.

(2) an interlayer of gelatin (80 mg./ft. Phenidone (l mg./ft.(incorporated developing agent), 2,5-di-tertoctylhydroquinone (20mg./ft. (oxidized color de veloper scavenger) and yellow filter dye1-(2,4,6-trichlorophenyl 3{3-[a-(2,4-di-tert-amylphenoxy)acetamido]benzamido}4-(4-methoxyphenylazo)-5-pyrazolone (75 mg./ft. and

(3) blue-sensitive, negative-working, gelatin-silver chlorobromideemulsion (150 mg./gelatin/ft. and 60 mg. silver/ft?) and magentacleavable Compound IV, 3-[4- (l hydroxy 4isopropoxy-Z-naphthylazo)phenylsulfonyl]-5-pentadecylhydroquinone (60mg./ft.

A sample of the photosensitive element is exposed to agraduated-density, multicolor test object. The following processingcomposition is employed in a pod and is spread between the exposedsurface of the photosensitive element and a superposed dyeimage-receiving element similar to that of Example 8 by passing thetransfer sandwich between a pair of juxtaposed pressure rollers:

G. Sodium hydroxide 20 Sodium sulfite l4 Hydroxyethylcellulose 25Potassium bromide 10 Water to 1 1.

(No developing agent is necessary in the processing composition since itis incorporated in the photosensitive element.) After 60 seconds atabout 25 C., the dye imagereceiving element is separated from thenegative element. A well-defined, negative, two-color magenta-yellowreproduction of the test object is observed on the dye image-receivingelement.

EXAMPLE 13 A photosensitive element is prepared by coating on an opaquecellulose acetate film support: (1) a negativeworking gelatin-silverbromide emulsion (300 mg. gelatin/ft? and 100 mg. silver/ft?) and cyandye-providing Compound VII (90 mg./ft. (this compound is colorless inthis state) and (2) gelatin overcoat (80 mg./ft.

A dye image-receiving element is prepared as in Example 8.

A sample of the photosensitive element is exposed and processed as inExample 8 employing the following processing composition: NaOH (1normal), Na SO g./l.), hydroxyethylcellulose g./l.) andN-methyl-paminophenol (0.9 g./l.).

After 60 seconds at 24 C., the film unit is separated. A negative cyandye image is observed on the dye imagereceiving sheet.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:

1. A photosensitive element comprising a support having thereon at leastone photosensitive silver halide emulsion layer, each said silver halideemulsion layer having 24 associated therewith a compound which iscleavable upon oxidation in an alkaline medium having the formula:

Ballasts (Sou-Dye),

wherein:

(1) each R represents hydrogen or a hydrolyzable moiety;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render said cleavablecompound nondiffusible during development in an alkaline processingcomposition;

(3) Dye is a dye or dye precursor;

(4) n is an integer of 1 to 3; and

(5) m is an integer of 1 to 3.

2. The photosensitive element of claim 1 wherein R is H,nislandmis1.

3. The photosensitive element of claim 1 wherein said compound which iscleavable upon oxidation in an alkaline medium is 3 4-4-phenylazobenzamido phenylsulfonyl] -5- pentadecylhydroquinone;

3- [4-( 1-hydroxy-4-isopropoxy-2-naphthylazophenylsulfonyl]-5-pentadecylhydroquinone;

3- 4-( l-phenyl-3-methylcarbamoyl-4-pyrazolin-5-onylazo) phenylsulfonyl-S-pentadecylhydroquinone;

3-{ 3- [2- 3 ,5 -dichloro -4-hydroxyphenylamino -4-benzamido-5-hydroxyphenylcarbamoyl] benzenesulfonyl}-5-pentadecylhydroquinone; or

2-chloro-3-{4- [4-( 1-phenyl-3-methylcarbamoyl-4-pyrazolin-5 -ony1azophenylsulfonamido] phenylsulfonyl}-5- pentadecylhydroquinone.

4. A photosensitive element comprising a support having thereon ared-sensitive silver halide emulsion layer having associated therewith acyan dye image-providing material, a green-sensitive silver halideemulsion layer having associated therewith a magenta dye image-providingmaterial, and a blue-sensitive silver halide emulsion layer havingassociated therewith a yellow dye imageproviding material, at least oneof said dye image-providmg materials being a compound which is cleavableupoln oxldation in an alkaline medium having the formu a:

Ballasts (S 2- y R wherein:

( 1) each R represents hydrogen or a hydrolyzable moiety;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render said cleavablecompound nondiifusible during development in an alkaline processingcomposition;

(3) Dye is a dye or dye precursor;

(4) n is an integer of 1 to 3; and

(5) m is an integer of l to 3.

5. The photosensitive element of claim 4 wherein R isH,nis 1 andmis l.

6. A photographic film unit which is adapted to be processed by passingsaid unit between a pair of juxtaposed pressure-applying memberscomprising:

(a) a photosensitive element comprising a support having thereon atleast one photosensitive silver halide emulsion layer, each said silverhalide emulsion layer having associated therewith a compound which iscleavable upon oxidation in an alkaline medium having the formula:

BallastrU-( 2 y )m wherein:

(1) each R represent hydrogen or a hydrolyzable moiety;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render said cleavablecompound nondiffusible during development in an alkaline processingcomposition;

( 3) Dye is a dye or dye precursor;

(4) n is an integer of l to 3; and

(5) m is an integer of 1 to 3;

(b) a dye image-receiving layer; and

(c) a rupturable container containing an alkaline processingcomposition, said container being adapted to be positioned duringprocessing of said film unit so that a compressive force applied to saidcontainer by said pressure-applying members will effect a discharge ofthe containers contents within said film unit;

said film unit containing a silver halide developing agent. 7. The filmunit of claim 6 wherein R is H, n is 1 and m is 1.

8. The film unit of claim 6 wherein said compound which is cleavableupon oxidation in an alkaline medium 18 3- [4-(4-phenylazobenzamido)phenylsulfonyl1-5- pentadecylhydroguinone;

3- 4- 1-hydroxy-4-isopropoxy-Z-naphthylazophenylsulfonyl]-5-pentadecylhydroquinone;

3- [4-1-phenyl-3-methylcarbamoyl-4-pyrazolin-S-onylazo)phenylsulfonyl]-5-pentadecylhydroquinone;

3-{3- [2- 3 ,5 -dichloro-4-hydroxyphenylamino-4-benzamido-S-hydroxyphenylcarbamoyl]benzenesulfonyl}5-pentadecylhydroquinone; or

2-chloro-3-{4- [4-( 1-phenyl-3-methylcarbamoyl-4-pyrazolin-S-onylazophenylsulfonamido phenylsulfonyl}- 5-pentadecylhydroquinone.

9. The film unit of claim 6 wherein said dye imagereceiving layer islocated in said photosensitive element between said support and thelowermost photosensitive silver halide emulsion layer.

10. The film unit of claim 6 wherein said dye imagereceiving layer iscoated on a separate support and is adapted to be superposed on saidphotosensitive element after exposure thereof.

11. The film unit of claim wherein said rupturable container is sopositioned during processing of said film unit that a compressive forceapplied to said container by said pressure-applying members will efiecta discharge of the containers contents between said dye image-receivinglayer and the outermost layer of said photosensitive element.

12. A photographic film unit which is adapted to be processed by passingsaid unit between a pair of juxtaposed pressure-applying memberscomprising:

(a) a photosensitive element comprising a support having thereon ared-sensitive silver halide emulsion layer having associated therewith acyan dye imageproviding material, a green-sensitive sliver halideemulsion layer having associated therewith a magenta dye image-providingmaterial, and a blue-sensitive silver halide emulsion layer havingassociated therewith a yellow dye image-providing material;

(b) a dye image-receiving layer; and

20 wherein:

(1) each R represents hydrogen or a hydrolyzable moiety; (2) Ballast isa photographically inert organic ballasting radical of such molecularsize and configuration as to render said cleavable compoundnondiffusible during development in an alkaline processing composition;

(3) Dye is a dye or dye precursor;

(4) n is an integer of 1 to 3; and

(5) m is an integer of 1 to 3.

13. The photographic film unit of claim 12 wherein R is H, n is 1 and mis 1 and said developing agent is contained in said rupturablecontainer.

14. A process for producing a photographic transfer image in colorcomprising:

(a) imagewise-exposing a photosensitive element comprising a supporthaving thereon at least one photosensitive silver halide emulsion layer,each said silver halide emulsion layer having associated therewith a dyeimage-providing material comprising a compound which is cleavable uponoxidation. in an alkaline medium having the formula:

Ballast T- y wherein:

(1) each R represents hydrogen or a hydrolyzable moiety;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render said cleavablecompound nondiffusible during development in an alkaline processingcomposition;

(3) Dye is a dye or dye precursor;

(4) n is an integer of 1 to 3;

(5) m is an integer of 1 to 3;

(b) treating said photosensitive element with an alkaline processingcomposition in the presence of a silver halide developing agent toeffect development of each of said exposed silver halide emulsionlayers, thereby oxidizing said developing agent;

(c) said oxidized developing agent thereby cross-oxidizing each saidcleavable compound to cause said compound to cleave at the S0 linkage,thus forming an imagewise distribution of diffusible dye or dyeprecursor containing the S0 moiety as a solubilizing group as a functionof said imagewise exposure of each of said silver halide emulsionlayers; and

(d) at least a portion of each of said imagewise distributions ofdifiusible dye or dye precursor containing said solubilizing groupdifiusing to a dye imagereceiving layer to provide said transfer image.

15. The process of claim 14 wherein said treatment step (b) is effectedby:

(a) superposing over the layer outermost from the support of saidphotosensitive element said dye image-receiving layer coated on asupport;

(b) positioning a rupturable container containing an alkaline possessingcomposition between said exposed photosensitive element and said dyeimagereceiving layer, said alkaline processing composition containingsaid developing agent; and

(c) applying a compressive force to said contained to effect a dischargeof the containers contents between said outermost layer of said exposedphotosensitive element and said dye image-receiving layer.

16. The process of claim 14 wherein R is H, n is 1 and m is 1.

17. The process of claim 14 wherein said compound which is cleavableupon oxidation in an alkaline medium 3- 4- 4-phenylazobenzamidophenylsulfonyl pentadecylhydroquinone;

3- [4- 1-hydroxy-4-isopropoxy-Z-naphthylazophenylsulfonyl]-S-pentadecylhydroquinone;

3- [4-( 1-phenyl-3 -methylcarbamoyl-4-pyrazolin-5- onylazo)phenylsulfonyl] -5-pentadecylhydroquinone 3-{3- [2- 3,5-dichloro-4-hydroxyphenylamino -4-benzamido-S-hydroxyphenylcarbamoyl]benzenesulfonyl}-5-pentadecylhydroquinone;or

2-chloro-3- 4- [4-( 1-phenyl-3-methylcarbamoyl-4-pyrazolin-S-onylazophenylsulfonamido] phenylsulfonyl} 5-pentadecylhydroquinone.

18. A process for producing a photographic transfer image in colorcomprising:

(a) imagewise-exposing a photosensitive element comprising a supporthaving thereon a red-sensitive silver halide emulsion layer havingassociated therewith a cyan dye image-providing material, agreen-sensitive silver halide emulsion layer having associated therewitha magenta dye image-providing material, and a blue-sensitive silverhalide emulsion layer having associated therewith a yellow dyeimage-provindg material, at least one of said dye image-providingmaterials comprising a compound which is cleavable upon oxidation in analkaline medium having the formula:

Ballast (sol-D e)m wherein:

(1) each R represents hydrogen or a hydrolyzable entity;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render said cleavablecompound nondifiusible during development in an alkaline processingcomposition;

(3) Dye is a dye or dye precursor;

,(4) n is an integer of 1 to 3; and

(5) m is an integer of 1 to 3;

(b) superposing over the layer outermost from the support of saidphotosensitive element a dye imagereceiving layer coated on a support;

(c) positioning a rupturable container containing an alkaline processingcomposition comprising a silver halide developing agent between saidexposed photosensitive element and said dye image-receiving layer;

(d) applying a compressive force to said container to elfect a dischargeof the containers contents between said outermost layer of said exposedphotosensitive element and said dye imagereceiving layer;

(e) thereby efiecting development of each of said exposed silver halideemulsion layers, thereby oxidizing said silver halide developing agent;

(f) said oxidized developing agent cross-oxidizing each said cleavablecompound to cause said compound to cleave at the S0 linkage, thusforming an imagewise distribution of diffusible dye or dye precursorcontaining the S0 moiety as a solubilizing group as a function of saidimagewise exposure of each of said silver halide emulsion layers;

(g) at least a portion of each of said imagewise distributions ofdiffusible dye or dye precursor containing said solubilizing groupdiffusing to said dye imagereceiving layer to provide said transferimage; and

(h) separating said photosensitive element from said dye image-receivinglayer coated on its said support.

19. The process of claim 18 wherein R is H, n is 1 and m is 1.

20. A process for producing a photographic transfer image in colorcomprising:

(A) imagewise-exposing a photosensitive element comprising a transparentsupport having thereon the following layers in sequence:

(a) a dye image-receiving layer;

(b) an alkaline solution-permeable, substantially opaquelight-reflective layer;

(c) a red-sensitive sliver halide emulsion layer having associatedtherewith a cyan dye imageproviding material;

,(d) a green-sensitive silver halide emulsion layer having associatedtherewith a magenta dye image-providing material; and

(e) a blue-sensitive silver halide emulsion layer having associatedtherewith a yellow dye imageproviding material;

at least one of said dye image-providing materials comprising a compoundwhich is cleavable upon oxidation in an alkaline medium having theformula:

Ballast (SN-Dye),

wherein:

(1) each R represents hydrogen or a hydrolyzable entity;

(2) Ballast is a photographically inert organic ballasting radical ofsuch molecular size and configuration as to render said cleavablecompound nonditlfusible during development in an alkaline processingcomposition;

(3) Dye represents a dye or dye precursor;

(4) n is an integer of 1 to 3; and

(5) m is an integer of 1 to 3;

.(B) developing each said exposed silver halide emulsion layer with asilver halide developing agent thereby causing said developing agent tobecome oxidized;

(C) said oxidized developing agent thereby cross-oxidizing each saidcleavable compound to cause said compound to cleave at the S0 linkage,thus forming an imagewise distribution of difiusible dye or dye pre- 2930 cursor containing the S0 moiety as a solubilizing References Citedgroup as a function of said imagewise exposure of UNITED STATES PATENTSeach of said silver halide emulsion layers; and 3,364,022 1/1968 Barr 963 (D) at least a portion of each of said imagewise distributions ofdilfusible dye or dye precursor contain- 5 JESSE BROWN Primary Examinerlng said solublhzing group dlffusing to said dye lmagereceiving layer toprovide said transfer image view- SURO' PICO, Assistant Examiner ablethrough said transparent support. U S Cl X R 21. The process of claim 20wherein R is H, n is 1 and m is 1. 10 96-29, 74, 76 C, 77

